CN104956529A - Electrode for lithium secondary battery, lithium secondary battery using same and method for manufacturing same - Google Patents
Electrode for lithium secondary battery, lithium secondary battery using same and method for manufacturing same Download PDFInfo
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- CN104956529A CN104956529A CN201380071727.2A CN201380071727A CN104956529A CN 104956529 A CN104956529 A CN 104956529A CN 201380071727 A CN201380071727 A CN 201380071727A CN 104956529 A CN104956529 A CN 104956529A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M4/00—Electrodes
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
An electrode for a lithium secondary battery, a lithium secondary battery using the same and a method for manufacturing the same are provided. The electrode for a lithium secondary battery comprises: a current collector; an electrode active material layer located on the current collector; and inorganic particles having two or more radical polymerization functional groups are dispersed on the electrode active material layer. Accordingly, since a polymerization reaction can directly occur between monomers and the inorganic particles in a precursor solution when a polymer electrolyte is formed by in-situ polymerization, an interface between the electrode and the electrolyte can be improved. In addition, the distribution of the polymer electrolyte within the electrode can be uniform. Therefore, improved life and highly efficient discharging can be exhibited when charging and discharging the lithium secondary battery.
Description
Technical field
The present invention relates to secondary cell, more specifically, relate to for the electrode introducing the inorganic particle with polymer functional group of lithium secondary battery, the lithium secondary battery using described electrode and preparation method thereof.
Background technology
Lithium secondary battery is a kind of secondary cell, and it can utilize external power source to be filled with energy, and has a lot of advantages, the nickel-cadmium cell such as used than routine or Ni-MH battery energy density is higher and the life-span is longer characteristic.Recently, owing to also having the appearance of motor vehicle except smart mobile phone and tablet personal computer (PC), the demand for the medium-sized and large-scale lithium ion battery that can store large energy increases.
Based on high ion-conductivity and low viscosity, the liquid electrolyte used in traditional lithium secondary battery has the advantage being suitable for the lithium secondary battery realizing high-power output and high power capacity.But the problem that liquid electrolyte has is due to inflammability and leak of liquid, its fail safe and life-span decline.Therefore, people are studying energetically and can replace liquid electrolyte and the polymer dielectric improving stability.
But such polymer dielectric is excellent in internal short-circuit and fail safe, but compares with liquid electrolyte, lower with the interfacial characteristics of electrode, also therefore has the internal resistance of high battery.Therefore, IR pressure drop (IR drop) increases, and capacity reduces, and the life-span reduces in the process of charging and discharging.In addition, when preparing polymer dielectric to improve interfacial characteristics by in-situ method, the electrolytical distribution in electrode may become uneven.
Therefore, the fail safe of battery can be guaranteed and the distribution of polymer dielectric in the interfacial characteristics equably between maintenance electrode and polymer dielectric and electrode, thus the technology realizing high-power output and high capacity characteristics is required.
Prior art document
Patent documentation
Prior art document one: Korean Unexamined Patent Application Publication 10-2008-0058197
Prior art document two: Korean Unexamined Patent Application Publication 10-2006-0039008
Summary of the invention
Technical problem
The present invention is designed to solve the problem, and object is to be provided for the electrode, the lithium secondary battery using this electrode and preparation method thereof that can improve the uniformity of the distribution of interfacial characteristics between electrode and polymer dielectric and electrode Inner electrolysis matter of lithium secondary battery.
Technical solution
In order to solve the problems of the technologies described above, one aspect of the present invention is provided for the electrode of lithium secondary battery.The described electrode for lithium secondary battery comprises collector, is arranged on the electrode active material layers on described collector and is dispersed in the inorganic particle comprising two or more radical polymerization functional groups in described active material layer.
Described polymer functional group can comprise carbon-to-carbon double bond, and described polymer functional group can comprise at least one group be selected from vinyl groups, acrylate group and methacrylate based group.
Described inorganic material can comprise any one oxide or two or more composite oxides that are selected from silicon (Si), aluminium (Al), tin (Sn), germanium (Ge), chromium (Cr), manganese (Mn), nickel (Ni), zinc (Zn), titanium (Ti), cobalt (Co), indium (In), cadmium (Cd), bismuth (Bi), lead (Pb) and vanadium (V).
Relative to described active material, described inorganic particle can have the content of 0.1-50 % by weight.
Described inorganic particle can have 50-2, the average grain diameter of 000nm.
In order to solve the problems of the technologies described above, another aspect of the present invention provides lithium secondary battery.Described lithium secondary battery comprises the polymer dielectric be arranged to positive electrode facing with each other and negative electrode and be arranged between described positive electrode and described negative electrode; at least one in wherein said positive electrode and described negative electrode is formed by the above-mentioned electrode for lithium secondary battery; in this article, polymer dielectric polymer be dispersed in inorganic particle chemical crosslinking in the active material layer of electrode.
Owing to comprising the polymerization of the monomer of two or more radical polymerization functional groups, described polymer can be formed.
The polymer functional group of described monomer can comprise carbon-to-carbon double bond, and the polymer functional group of monomer can comprise at least one group being selected from vinyl groups, acrylate group and methacrylate based group.
In order to solve the problems of the technologies described above, another aspect of the present invention provides the method preparing lithium secondary battery.The described method preparing lithium secondary battery comprises: arrange positive electrode and negative electrode, makes it facing with each other; Injection of polymer electrolyte precursor solution between described positive electrode and described negative electrode, it comprises monomer, polymerization initiator and the organic electrolyte solution with two or more radical polymerization functional groups; And be polymerized described monomer at precursor solution situ, to form polymer dielectric, and at least one in described positive electrode and described negative electrode is formed by the above-mentioned electrode for lithium secondary battery.
Beneficial effect
According to the present invention, once form described polymer dielectric due to in-situ polymerization, direct polymerization reaction can occur between the monomer in inorganic particle and precursor solution, and the interfacial characteristics between described electrode and described electrolyte can improve.In addition, the distribution of the polymer dielectric in described electrode can become even.Therefore, in the process of the charging and discharging of lithium secondary battery, life-span and the efficient discharge characteristic of prolongation can be demonstrated.
In addition, lithium secondary battery prepared in accordance with the present invention can be prepared in the structure with pliability and various shape, and without the risk of electrolyte leakage.
Herein, effect of the present invention is not limited to above-mentioned effect, and other effect do not described above can be understood by those of ordinary skill in the art.
Accompanying drawing explanation
Fig. 1 is presented at the schematic diagram forming the method for polymer dielectric when use carries out in-situ polymerization for the electrode of secondary cell according to embodiments of the present invention;
Fig. 2 is the SEM image of the silica dioxide granule of the sizes being presented at preparation in experimental example 1;
Fig. 3 is the FT-IR spectrum of the silica dioxide granule of preparation in experimental example 1;
Fig. 4 is the FT-IR spectrum of the silica dioxide granule of preparation in experimental example 2;
Fig. 5 is the SEM image of negative electrode prepared by display experimental example 3;
Fig. 6 is the SEM image of positive electrode prepared by display experimental example 4;
Fig. 7 and Fig. 8 is that experimental example 5 situ is polymerized the native graphite negative electrode after preparing and LiNi
0.5mn
1.5o
4the SEM image of positive electrode;
Fig. 9 is the figure of the discharge capacity representing the battery based on circulation prepared by experimental example 6 and comparative example 1;
Figure 10 is the figure of the relative discharge capacity representing the battery based on current density prepared by experimental example 6 and comparative example 1;
Figure 11 is the figure of the discharge capacity representing the battery based on circulation prepared by experimental example 7 and comparative example 2; And
Figure 12 is the figure of the relative discharge capacity of the battery based on current density prepared by display experimental example 7 and comparative example 2.
Working of an invention mode
Hereinafter, with reference to accompanying drawing, exemplary embodiment of the subject disclosure is described in detail.But should be appreciated that, have no intention the present invention to be limited to particular forms disclosed, just the opposite, all modifications in the spirit and scope of the present invention, equivalent and alternative form are contained in the present invention.
It is to be further understood that when using in this manual, term " is configured at ... (on) " existence of refering in particular to described layer, film, region, plate and/or analog above, but also comprise be set directly at above and get involved another part therebetween.In addition, it will also be understood that, direction term " above (above) ", " (upper) (part) above ", upper surface (upper surface) and/or similar also can be understood to " following (below) ", " (lower) (part) below ", lower surface (lower surface) and/or similar.That is direction in space should be understood to relative direction, and should not be understood to be restricted to absolute direction.
As used herein, " one ", " one " and " described " of singulative is intended to also comprise plural form, unless context clearly indicates in addition.Also will understand, when using in this manual, term " comprises/comprises (comprises and/or comprising) " existence of refering in particular to described feature, integer, step, operation, element and/or parts, but does not get rid of and exist or one or more further feature additional, integer, step, operation, element, parts and/or their group.
In the drawings, the thickness in layer and region is shown so that illustrate, and may be exaggerated relative to the physical thickness of reality.When compiling label to the structure member of every width figure, although label is shown in different drawings, in whole accompanying drawing describes, identical numeral can refer to similar element.
In addition, in the following description and the drawings, when unnecessary details makes the present invention not know, the detailed description of known function or structure will be omitted.
The availability of the electrode for electrochemical appliance (particularly lithium secondary battery) is provided as according to the electrode of embodiment of the present invention.Described electrode comprises collector, is arranged on the electrode active material on described collector and is dispersed in the inorganic particle comprising two or more radical polymerization functional groups in active material layer.
That is described inorganic particle may reside under they are scattered in the inside of active material layer or the state on surface, and described inorganic particle can by two or more functional group modification wherein can carrying out Raolical polymerizable.
In preferred embodiments, polymer functional group can comprise carbon-to-carbon double bond, and more preferably, can comprise any one group of the methacrylate based group being selected from vinyl groups, acrylate group and having terminal double bond.
The inorganic material forming inorganic particle is had no particular limits, as long as it is easily modified as polymer functional group.Such as, inorganic material can be provided as metal or metalloid oxide type, and preferably, can be any one oxide or two or more composite oxides being selected from silicon (Si), aluminium (Al), tin (Sn), germanium (Ge), chromium (Cr), manganese (Mn), nickel (Ni), zinc (Zn), titanium (Ti), cobalt (Co), indium (In), cadmium (Cd), bismuth (Bi), lead (Pb) and vanadium (V).
Such metal oxide or quasi-metal oxide can be formed due to the condensation of metal alkoxide or metalloid alkoxide.Such as, silicon dioxide can use the hydrolysis of vinyltrimethoxy silane and dehydration synthesis to be formed.In another embodiment, aluminium oxide can use the hydrolysis of aluminium isopropoxide and dehydration synthesis to be formed, and work as obtained aluminium oxide and vinyltrimethoxy silane when reacting, the inorganic particle of the composite oxides type of aluminium oxide and silicon dioxide can be formed.In addition, based on other such as acrylate group (acrilate) of introducing and/or the radical polymerization functional group of similar group but not the vinyl groups of vinyltrimethoxy silane, the polymer functional group of inorganic particle can be formed by multiple material.
Inorganic particle is mixed and after being dispersed in the electrode slurry comprising negative or positive electrode active material, comprise the inorganic particle of polymer functional group described in applied on collector.In addition, described electrode slurry can comprise for stable slurry and improve adhesive adhesive and the electric conducting material for improving conductivity.
Described positive electrode active materials can be selected from multiple material, such as LiMO
2(M=V, Cr, Co, Ni), LiM
2o
4(M=Mn, Ti, V), LiMPO
4(M=Co, Ni, Fe, Mn), LiNi
1-xco
xo
2(0<x<1), LiNi
2-xmn
xo
4(0<x<2), Li [NiMnCo] O
2and/or similar material, and positive electrode active materials can have based on the layer structure of used active material, spinel structure or olivine structural.Negative active core-shell material can be selected from material with carbon element, such as graphite or hard carbon; Metal material, such as lithium (Li), sodium (Na), magnesium (Mg), aluminium (Al), silicon (Si), indium (In), titanium (Ti), plumbous (Pb), gallium (Ga), germanium (Ge), tin (Sn), bismuth (Bi), antimony (Sb) or their alloy; And titanium (Ti) base oxide, such as lithium titanate (Li
4ti
5o
12).In this article, for may be used for positive pole of the present invention and negative active core-shell material has no particular limits.
Collector can be conductive board, and it supports the electrode active material layers being wherein dispersed with the inorganic particle with polymer functional group, and can be selected from aluminium, copper, gold, nickel and/or analog.
Meanwhile, the content of inorganic particle can be set in the scope of 0.1-50 % by weight.When the content of inorganic particle is too low (as will be described hereinafter), possibly cannot by the effect obtaining enough raising crosslink densities that combines with the polymer be included in polymer dielectric, and when the content of inorganic particle is too high, the capacity of described lithium secondary battery and energy density may be lowered.
The average grain diameter of inorganic particle can in the scope of 50-2,000nm.When the size of inorganic particle is greater than the size of the active material forming electrode active material layers, described inorganic particle can not disperse effectively in electrode, and electrode density also may be lowered, and the performance of battery also may be lowered.
According to another embodiment of the invention, provide and use the above-mentioned electrode for lithium secondary battery as lithium secondary battery one of at least in positive electrode and negative electrode.
Especially, comprise according to the lithium secondary battery of embodiment of the present invention and be arranged to positive electrode facing with each other and negative electrode, and the polymer dielectric be arranged between positive electrode and negative electrode, and at least one inorganic particle be dispersed in described active material layer comprising collector, be arranged on the electrode active material layers on described collector and comprise two or more radical polymerization functional groups in positive electrode and negative electrode.According to above-mentioned lithium secondary battery, the polymer of polymer dielectric can be present in the active material layer of electrode with the state of the inorganic particle chemical crosslinking be dispersed in active material layer.
The detailed description of collector, electrode active material and inorganic particle and identical described in the electrode for lithium secondary battery.
In this article, the polymer of polymer dielectric can be formed due to the polymerization comprising the monomer of two or more radical polymerization functional groups.In preferred embodiments, the polymer functional group of monomer can comprise carbon-to-carbon double bond, and more preferably, can comprise at least one group being selected from vinyl groups, acrylate group and methacrylate based group.In another embodiment, described monomer can be the aklylene glycol base monomer in conjunction with above-mentioned polymer functional group, such as ethylene glycol or propylene glycol.
Meanwhile, according to another embodiment of the invention, provide the preparation method of above-mentioned lithium secondary battery.
The preparation method of described lithium secondary battery comprises and arranges positive electrode and negative electrode, makes it facing with each other; Injection of polymer electrolyte precursor solution between positive electrode and negative electrode, it comprises monomer, polymerization initiator and the organic electrolyte solution with two or more radical polymerization functional groups; And be polymerized described monomer at precursor solution situ, to form polymer dielectric.In this article, at least one inorganic particle with two or more radical polymerization functional groups comprising collector, electrode active material layers is on a current collector set and is dispersed in described active material layer in described positive electrode and described negative electrode.
The detailed description of collector, electrode active material and inorganic particle and identical described in the electrode for lithium secondary battery.
The organic solution of polymer electrolyte precursor solution can comprise electrolyte solvent and electrolytic salt.Described solvent can be selected from ethylene carbonate ester, carbonic acid 1,2-sub-propyl ester, dimethyl carbonate, methyl ethyl carbonate, ethyl propionate, dimethoxy-ethane, diethoxyethane, oxolane, gamma-butyrolacton and the mixture of two or more thereof.Described electrolytic salt can be selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), trifluoromethanesulfonic acid lithium (LiCF
3sO
3), hexafluoroarsenate lithium (LiAsF
6), di-oxalate lithium borate (LiBOB) and two trifluoromethanesulfonimide lithium (lithiumtrifluoromethansulfonylimide; LiTFSI) at least one lithium salts.In this article, other known electrolyte solvent and electrolytic salt can also be used.
In addition, in order to accelerated reaction, polymer electrolyte precursor solution can comprise very small amount of common polymerization initiator if desired, such as azodiisobutyronitrile (AIBN), acetyl peroxide (acetylperoxide), benzoyl peroxide (benzoylperoxide) and/or analog.
Fig. 1 is presented at the schematic diagram using and form the method for polymer dielectric when carrying out in-situ polymerization according to the electrode for lithium secondary battery of embodiment of the present invention.
As described in reference to fig. 1, the active material layer 20 comprising electrode active material 22 is arranged on collector 10, and the inorganic particle 30 with polymer functional group is disperseed and is configured in described active material layer 20.When polymer electrolyte precursor solution is injected into, described active material layer 20 flood by described precursor solution, and the monomer 40 in described precursor solution has mobility, and is dispersed in described active material layer 20.
Then, described monomer 40 grows up to polymer chain in the polymerization, and in this article, the inorganic particle 30 with polymer functional group be present in active material layer 20 also adds polymerization reaction.Therefore, the polymer formed by home position polymerization reaction can have network configuration 50, and itself and inorganic particle are in multiple linking point (link point) place's chemical crosslinking.
According to above, react with the direct polymerization of described inorganic particle 30 because the monomer 40 in polymerization reaction in electrolyte precursor solution causes, the adherence between described electrode and described polymer dielectric and interface stability can be improved.In addition, the distribution due to the polymer dielectric in electrode becomes even, and the performance of described battery can improve.
In order to help the understanding of the present invention, give preferred experimental example hereinafter.But experimental example is below only for helping the understanding of the present invention, and the present invention is not defined to following experimental example.
There is the synthesis of the inorganic material of polymer functional group
Experimental example 1
At room temperature, the pure water of 150ml is inserted in reactor, and the vinyltrimethoxy silane of quantitative 10ml, to make it slowly be added dropwise in described reactor, and stir.Vinyltrimethoxy silane be dispersed in completely purify waste water interior after become transparent, to add in the ammonia solution of 0.1ml and at room temperature to stir 12 hours to carry out condensation polymerization.After having reacted, centrifuge is used to prepare sediment from the liquid obtained.With methyl alcohol by sediment undergoes washing three times or more, and to filter, thus remove unreacted material and impurity.By obtained sediment at 70 DEG C dry 1 hour in vacuum drying oven, obtain silicon dioxide, it has the size of 1.2 μm, and can be polymerized.
In addition, can said method be adopted to synthesize with sizes by the silicon dioxide be polymerized.First salpeter solution is introduced in purifying waste water, and react.
Detailed reaction condition describes in Table 1 with the size of the silica dioxide granule obtained.
[table 1]
Be described through the SEM image of the silica dioxide granule of sizes prepared by experimental example 1 in fig. 2.With reference to figure 2, the silica dioxide granule of sizes is formed uniformly.
Fig. 3 is the FT-IR spectrum of the silica dioxide granule prepared by experimental example 1.Should be appreciated that and also exist about 1,600cm
-1-Isosorbide-5-Nitrae 00cm
-1infrared absorbance range in can carry out with silica dioxide granule the vinyl groups that synthesizes.
Experimental example 2
The inorganic material of non-silicon dioxide and vinyltriethoxysilane or 3-(triethoxysilicane alkyl) propyl methacrylate react, vinyl groups or acrylate group to be incorporated on the surface of multiple inorganic particle.
Aluminium isopropoxide is dispersed in water, and stirs.Salpeter solution adds as catalyst, and reacts 6 hours at 90 DEG C, forms alumina particle thus.Then, to stir after 1 hour at 90 DEG C in introducing vinyltriethoxysilane or 3-(triethoxysilicane alkyl) propyl methacrylate, sediment is cleaned, obtains final product
Fig. 4 is the FT-IR spectrum of silica dioxide granule prepared by experimental example 2.Should be appreciated that and also exist about 1,630cm
-1-Isosorbide-5-Nitrae 00cm
-1infrared absorbance range in can carry out with alumina particle the vinyl groups that synthesizes.
In identical method, by identical method, polymerization organo-functional group is introduced in multiple inorganic material, such as titanium, germanium and/or analog.
Preparation comprises the electrode of the inorganic material with polymer functional group
Experimental example 3
Use native graphite for the preparation of the negative electrode of lithium secondary battery.DAG-A active material (it is native graphite) and the silicon dioxide with vinyl groups synthesized in experimental example 1 are disperseed by being dry mixed to close.KS6 and Super-P (it is electric conducting material), adhesive PVdF and solvent NMP are introduced into prepare electrode slurry.Aluminium foil applies described electrode slurry, and solvent is taken out from the vacuum drying oven of 120 DEG C, thus complete electrode.
Experimental example 4
Adopt the method identical with the method preparing negative electrode of experimental example 3 for the preparation of the positive electrode of lithium secondary battery, difference is LiNi
0.5mn
1.5o
4be used as electrode active material.
Respectively with reference to figure 5 and Fig. 6, describe and be presented at the negative electrode of preparation and the SEM image of positive electrode in experimental example 3 and experimental example 4.With reference to figure 5 and Fig. 6, silica dioxide granule is disperseed, and is present in electrode active material.
Adopt the electrolytical in-situ polymerization that the electrode comprising the inorganic material with synthesis functional group carries out
Experimental example 5
At 1M LiPF
6in the electrolyte solution of EC/DEC=1/1, stir monomer and the AIBN (it is initator) of diethylene glycol double methacrylate, thus preparation can form the electrolyte solution of polyeletrolyte by in-situ polymerization.After using the electrode of preparation in experimental example 3 and experimental example 4 to prepare battery, then inject described electrolyte solution, and carry out the home position polymerization reaction of a hour at the temperature of 90 DEG C, thus prepare lithium secondary battery.
In position after polymerization, with reference to figure 7 and Fig. 8, to native graphite negative electrode and LiNi
0.5mn
1.5o
4the SEM image of positive electrode is described.Because the content with the silicon dioxide of vinyl groups increases, the surface of described electrode active material is utilized the polymer dielectric that in-situ polymerization formed and is coated with equably.Therefore, in position in polymerization process, the silicon dioxide with vinyl groups adds reaction, to improve adhesiveness between described electrode and described electrolyte and interface stability.
The evaluation of the electrochemical properties of negative electrode
Experimental example 6
Use the native graphite negative electrode, the LiFePO that mix with the silicon dioxide with vinyl groups
4the 1M LiPF mixed with diethylene glycol bis-acrylate monomer in positive electrode and in-situ method
6the electrolyte solution of EC/DEC=1/1 prepares battery.
Comparative example 1
Prepare battery with the method identical with experimental example 6, difference is that the silicon dioxide with vinyl groups is not introduced into negative electrode.
The electrochemical properties of battery prepared by experimental example 6 and comparative example 1 is evaluated, and describes result with reference to Fig. 9 and Figure 10.Fig. 9 current density shown in 2.0-3.7V voltage range is the result of the charge/discharge experiment of 0.5C, and Figure 10 current density shown within the scope of 2.0-3.7V is the result of the discharge test of 0.1-2.0C.
With reference to figure 9, compared with wherein not using the situation of silicon dioxide, the situation that the silicon dioxide with vinyl groups is introduced into negative electrode demonstrates capacitance of lithium secondary battery for the improvement of circulation and life characteristic.Especially, relative to active material, when the amount of the silicon dioxide with vinyl groups is 4 % by weight, the interfacial characteristics between described electrolyte and described negative electrode obtains best improvement, and shows the result of the optimum of discharge capacity and life characteristic.In addition, with reference to Figure 10,4 % by weight time, the most effective high rate performance (rate capability) is shown.
The evaluation of the electrochemical properties of positive electrode
Experimental example 7
Use the LiNi mixed with the silicon dioxide with vinyl groups
0.5mn
1.5o
4positive electrode, lithium metal negative electrode and the 1M LiPF mixed with diethylene glycol bis-acrylate monomer
6the electrolyte solution of EC/DEC=1/1, prepares battery with in-situ method.
Comparative example 2
Adopt the method identical with experimental example 7 to prepare battery, difference is that the silicon dioxide with vinyl groups is not introduced into negative electrode.
The electrochemical properties of battery prepared by experimental example 7 and comparative example 2 is evaluated, and with reference to Figure 11 and Figure 12, result is described.Figure 11 current density be presented in 3.0-4.9V voltage range is the result of the charge/discharge experiment of 0.5C, and Figure 12 current density range shown within the scope of 2.0-4.9V is the result of the discharge test of 0.1-2.0C.
With reference to Figure 11, compared with not using the situation of silicon dioxide, the situation that the silicon dioxide wherein with vinyl groups is incorporated into positive electrode demonstrates the capacity of lithium secondary battery for the improvement of circulation and the result of life characteristic.Especially, relative to active material, when the amount of the silicon dioxide with vinyl groups is 4 % by weight, the interfacial characteristics between described electrolyte and described negative electrode obtains best improvement, and shows the result of the optimum of discharge capacity and life characteristic.In addition, with reference to Figure 12,4 % by weight time, the most effective flash-over characteristic is shown.
To those skilled in the art, obviously multiple amendment can be carried out to above-mentioned exemplary of the present invention, and do not depart from the spirit or scope of the present invention, and the present invention is intended to contain all amendments like this, if they fall into appended claims and equivalent thereof scope within.
To the description of the label of main element in accompanying drawing
10: collector
20: electrode active material layers
22: active material
30: inorganic particle
40: monomer
50: polymer-inorganic particle network
Claims (11)
1., for the electrode of lithium secondary battery, it comprises
Collector;
Be arranged on the electrode active material layers on described collector; And
Be dispersed in the inorganic particle comprising two or more radical polymerization functional groups in described active material layer.
2. the electrode for lithium secondary battery of claim 1, wherein polymerizable functional group comprises carbon-to-carbon double bond.
3. the electrode for lithium secondary battery of claim 1, wherein said polymer functional group comprises at least one group being selected from vinyl groups, acrylate group and methacrylate based group.
4. the electrode for lithium secondary battery of claim 1, wherein inorganic material comprises any one oxide or two or more composite oxides that are selected from Si, Al, Sn, Ge, Cr, Mn, Ni, Zn, Ti, Co, In, Cd, Bi, Pb and V.
5. the electrode for lithium secondary battery of claim 1, wherein relative to described active material, the content of described inorganic particle is in the scope of 0.1-50 % by weight.
6. the electrode for lithium secondary battery of claim 1, the average grain diameter of wherein said inorganic particle is in the scope of 50-2,000nm.
7. lithium secondary battery, it comprises:
The positive electrode of setting facing with each other and negative electrode; And
Be arranged on the polymer dielectric between described positive electrode and described negative electrode,
Wherein, at least one electrode defined by any one in claim 1-6 in described positive electrode and described negative electrode is formed, and
Polymer and the inorganic particle chemical crosslinking be dispersed in the described active material layer of described electrode of wherein said polymer dielectric.
8. the lithium secondary battery of claim 7, wherein said polymer by comprise two or more radical polymerization functional groups monomer polymerization and formed.
9. the lithium secondary battery of claim 8, the polymer functional group of wherein said monomer comprises carbon-to-carbon double bond.
10. the lithium secondary battery of claim 8, the polymer functional group of wherein said monomer comprises at least one group being selected from vinyl groups, acrylate group and methacrylate based group.
11. methods preparing lithium secondary battery, it comprises:
By positive electrode and negative electrode setting facing with each other;
Injection of polymer electrolyte precursor solution between described positive electrode and described negative electrode, described precursor solution comprises monomer, polymerization initiator and the organic electrolyte solution with two or more radical polymerization functional groups; And
Described monomer is polymerized at described precursor solution situ, to form polymer dielectric,
Wherein, at least one electrode defined by any one in claim 1-6 in described positive electrode and described negative electrode is formed.
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| Application Number | Priority Date | Filing Date | Title |
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| KR20120146112A KR101511412B1 (en) | 2012-12-14 | 2012-12-14 | Electrode for lithium secondary battery, lithium secondary battery using the same and fabrication method thereof |
| KR10-2012-0146112 | 2012-12-14 | ||
| PCT/KR2013/009704 WO2014092330A1 (en) | 2012-12-14 | 2013-10-30 | Electrode for lithium secondary battery, lithium secondary battery using same and method for manufacturing same |
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| CN104956529A true CN104956529A (en) | 2015-09-30 |
| CN104956529B CN104956529B (en) | 2018-12-14 |
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| CN201380071727.2A Expired - Fee Related CN104956529B (en) | 2012-12-14 | 2013-10-30 | For lithium secondary battery electrode, use lithium secondary battery of the electrode and preparation method thereof |
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| Country | Link |
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| KR (1) | KR101511412B1 (en) |
| CN (1) | CN104956529B (en) |
| WO (1) | WO2014092330A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107112542A (en) * | 2014-12-17 | 2017-08-29 | 日立化成株式会社 | Lithium rechargeable battery |
| CN110098386A (en) * | 2018-01-29 | 2019-08-06 | 罗伯特·博世有限公司 | The active material of solid electrolyte interface with covalent bonding |
| CN112652756A (en) * | 2019-10-11 | 2021-04-13 | 通用汽车环球科技运作有限责任公司 | In-situ polymerization protected lithium metal electrode |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102596721B1 (en) * | 2017-05-26 | 2023-10-31 | 베이징사범대학교 | Flexible all-solid lithium ion secondary battery and method of manufacturing the same |
| US11710852B2 (en) | 2018-02-09 | 2023-07-25 | Lg Energy Solution, Ltd. | Separator for secondary battery and lithium secondary battery including same |
| WO2020018731A1 (en) * | 2018-07-18 | 2020-01-23 | Nanotek Instruments, Inc. | Fast-chargeable lithium battery electrodes |
| US11870051B2 (en) | 2018-07-18 | 2024-01-09 | Global Graphene Group, Inc. | Method of improving fast-chargeability of a lithium-ion battery |
| CN113258132B (en) * | 2021-05-11 | 2022-09-06 | 合肥工业大学 | Solid electrolyte, preparation method thereof and solid battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070119894A (en) * | 2006-06-16 | 2007-12-21 | 주식회사 엘지화학 | Radical electrode active material having high density and electrochemical device using the same |
| KR100790852B1 (en) * | 2006-12-13 | 2008-01-03 | 삼성에스디아이 주식회사 | Anode, method of preparing the same, and lithium battery containing the anode |
| CN101164184A (en) * | 2005-04-19 | 2008-04-16 | 株式会社Lg化学 | Safety-improved electrode by introducing crosslinkable polymer and electrochemical device comprising the same |
| CN101195670A (en) * | 2006-09-25 | 2008-06-11 | 株式会社Lg化学 | Gel-typed polymer electrolyte containing diacryl amide-based polymeric material and electrochemical device comprising the same |
| CN102237528A (en) * | 2010-04-30 | 2011-11-09 | 三星Sdi株式会社 | Conductive agent, positive electrode slurry composition for lithium secondary battery including the conductive agent, and lithium secondary battery including the conductive agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110241A (en) * | 2000-09-29 | 2002-04-12 | Sharp Corp | Lithium polymer secondary battery and its production method |
| KR20120006730A (en) * | 2010-07-13 | 2012-01-19 | 엘지이노텍 주식회사 | Process for preparing lithium polymer secondary batteries employing gel polymerelectrolyte |
| KR101384881B1 (en) * | 2010-11-02 | 2014-04-15 | 한국전자통신연구원 | Lithium rechargeable battery |
-
2012
- 2012-12-14 KR KR20120146112A patent/KR101511412B1/en not_active IP Right Cessation
-
2013
- 2013-10-30 CN CN201380071727.2A patent/CN104956529B/en not_active Expired - Fee Related
- 2013-10-30 WO PCT/KR2013/009704 patent/WO2014092330A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164184A (en) * | 2005-04-19 | 2008-04-16 | 株式会社Lg化学 | Safety-improved electrode by introducing crosslinkable polymer and electrochemical device comprising the same |
| KR20070119894A (en) * | 2006-06-16 | 2007-12-21 | 주식회사 엘지화학 | Radical electrode active material having high density and electrochemical device using the same |
| CN101195670A (en) * | 2006-09-25 | 2008-06-11 | 株式会社Lg化学 | Gel-typed polymer electrolyte containing diacryl amide-based polymeric material and electrochemical device comprising the same |
| KR100790852B1 (en) * | 2006-12-13 | 2008-01-03 | 삼성에스디아이 주식회사 | Anode, method of preparing the same, and lithium battery containing the anode |
| CN102237528A (en) * | 2010-04-30 | 2011-11-09 | 三星Sdi株式会社 | Conductive agent, positive electrode slurry composition for lithium secondary battery including the conductive agent, and lithium secondary battery including the conductive agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107112542A (en) * | 2014-12-17 | 2017-08-29 | 日立化成株式会社 | Lithium rechargeable battery |
| CN107112542B (en) * | 2014-12-17 | 2021-01-26 | 昭和电工材料株式会社 | Lithium ion secondary battery |
| CN110098386A (en) * | 2018-01-29 | 2019-08-06 | 罗伯特·博世有限公司 | The active material of solid electrolyte interface with covalent bonding |
| CN112652756A (en) * | 2019-10-11 | 2021-04-13 | 通用汽车环球科技运作有限责任公司 | In-situ polymerization protected lithium metal electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101511412B1 (en) | 2015-04-10 |
| WO2014092330A1 (en) | 2014-06-19 |
| KR20140078027A (en) | 2014-06-25 |
| CN104956529B (en) | 2018-12-14 |
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